Process for the removal of volatile organic compounds from a fluid stream

ABSTRACT

A process claimed for the removal of VOCs from fluid streams. The process comprises a vacuum swing adsorption zone containing at least 2 adsorption beds wherein the adsorbent beds are cocurrently purged with a diluent stream comprising an inert gas prior to a countercurrent evacuation step. In addition, the adsorbent beds may contain a first adsorption layer comprising an adsorbent selective for the adsorption of the inert gas, whereby the inert gas is retained within the VSA system to prevent the creation of an explosive mixture upon the condensation of the desorbed VOCs.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Ser. No. 08/151,244,filed Nov. 12, 1993, now U.S. Pat. No. 5,415,682, hereby incorporated byreference.

FIELD OF THE INVENTION

This invention relates to a process for removing volatile organiccompounds (VOCs) from a fluid stream. More particularly, this inventionrelates to the use of a vacuum swing adsorption (VSA) process to removehighly flammable VOCs from a fluid stream with a minimum risk ofexplosion.

BACKGROUND OF THE INVENTION

The removal of a sorbable component from a gas or vapor stream byflowing such stream through a body of adsorbent material is afundamental engineering practice. One type of sorbable components whichare desirable to remove from a gas stream is volatile organic compoundsVOCs.

VOCs are formed in large quantities but at relatively low concentrationsfrom gas turbines, cogeneration plants, petrochemical plants, and inmany industrial processes where waste gases contain such materials asvapors of various solvents, inks, paints, and so forth. VOCs contain notonly hydrocarbons--saturated, unsaturated, and aromatic--but alsocontain oxygenated materials such as alcohols, esters, ethers, andacids, nitrogen containing compounds (principally amines), sulfurcontaining materials (mercaptans and thioethers) and halogen-containingmaterials, especially chlorine-substituted hydrocarbons but also organicfluorides and bromides. The presence of these VOCs in the gas stream canpresent a health risk or cause the gas stream to have an unpleasantodor.

The widespread use of solvents in industrial applications has resultedin increased emissions of VOCs into the atmosphere, giving rise toenvironmental concerns and prompting stricter legislative controls onsuch emissions. As a consequence, manufacturers of pharmaceuticals,coated products, textiles, and polymer composites and foams, as well ashydrocarbon producers and distributors, face a dilemma in removing VOCsfrom process gas streams in that, owing to rising energy prices,recovery costs are very often higher than the value of the VOCsrecovered, even in light of rising solvent prices. This dilemma has ledto inquiries into more profitable methods of removing condensableorganic vapors from process gas streams. A recent article titled,"Select the Best VOC Control Strategy," by Edward N. Ruddy and Leigh AnnCarroll which appeared in the July 1993 issue of "Chemical EngineeringProgress," pages 28-35 summarized current emission control options ofthermal oxidation, catalytic oxidation, condensation, carbon adsorptionand absorption. In the article, Ruddy and Carroll state that VOCs areamong the most common pollutants emitted by the chemical processindustries and the reduction of VOCs is, therefore, a majorenvironmental activity.

Conventional adsorption systems for solvent recovery from humid airtypically are operated until the solvent concentration in the outlet gasstream reaches a detectable preset breakthrough level whereupon the gasflow to the adsorber is stopped. The adsorbent bed then containssolvent, other condensable organic contaminants, and some amount ofwater which depends on the inlet relative humidity of the solvent ladengas stream. At this point, present-day techniques involve theintroduction of a hot inert gas or steam, either saturated orsuperheated, which displaces the solvent from the adsorbent to produce asolvent/water mixture upon condensation. Typically two adsorber beds areused, where one is adsorbing while the other bed undergoes regeneration.More recent technology for regenerating and recovering solvent fromadsorbent beds involves the use of inert gases (though for somesolvents, air also can be used) and low temperature condensation of thesolvent from the regenerating gas.

The removal of volatile organic compounds (VOC) from air by adsorptionis most often accomplished by thermal swing adsorption (TSA). Airstreams needing treatment can be found in most chemical andmanufacturing plants, especially those using solvents. At concentrationlevels from 500 to 15,000 ppm, recovery of VOCs from air is economicallyjustified. Steam is used to thermally regenerate activated carbonadsorbent. Concentrations above 15,000 ppm are typically in theexplosive range and require the use of a hot inert gas rather than airfor regeneration. Below about 500 ppm, recovery is not economicallyjustifiable, but environmental concerns often dictate adsorptiverecovery followed by destruction. Activated carbon is the traditionaladsorbent for these applications, which represent the second largest usefor gas phase carbons. U.S. Pat. No. 4,421,532 discloses a process forthe recovery of VOCs from industrial waste gases by thermal swingadsorption including the use of hot inert gases circulating in a closedcycle to desorb the VOCs.

Pressure swing adsorption (PSA) processes provide an efficient andeconomical means for separating a multi-component gas stream containingat least two gases having different adsorption characteristics. The morestrongly adsorbed gas can be an impurity which is removed from the lessstrongly adsorbed gas which is taken off as product, or, the morestrongly adsorbed gas can be the desired product which is separated fromthe less strongly adsorbed gas. For example, it may be desired to removecarbon monoxide and light hydrocarbons from a hydrogen-containingfeedstream to produce a purified (99+%) hydrogen stream for ahydrocracking or other catalytic process where these impurities couldadversely affect the catalyst or the reaction. On the other hand, it maybe desired to recover more strongly adsorbed gases, such as ethylene,from a feedstream to produce an ethylene-rich product.

In PSA processes, a multi component gas is typically passed to at leastone of a plurality of adsorption zones at an elevated pressure effectiveto adsorb at least one component, i.e. the more strongly adsorbedcomponents, while at least one other component passes through, i.e. theless strongly adsorbed components. At a defined time, the passing offeedstream to the adsorber is terminated and the adsorption zone isdepressurized by one or more cocurrent depressurization steps whereinthe pressure is reduced to a defined level which permits the separated,less strongly adsorbed component or components remaining in theadsorption zone to be drawn off without significant concentration of themore strongly adsorbed components. Then, the adsorption zone isdepressurized by a countercurrent depressurization step wherein thepressure in the adsorption zone is further reduced by withdrawingdesorbed gas countercurrently to the direction of the feedstream.Finally, the adsorption zone is purged and repressurized. Such PSAprocessing is disclosed in U.S. Pat. No. 3,430,418, issued to Wagner,U.S. Pat. No. 3,564,816, issued to Batta, and in U.S. Pat. No.3,986,849, issued to Fuderer et al., wherein cycles based on the use ofmulti-bed systems are described in detail. As is generally known anddescribed in these patents, the contents of which are incorporatedherein by reference as if set out in full, the PSA process is generallycarried out in a sequential processing cycle that includes each bed ofthe PSA system. A VSA process employs a similar sequential processingcycle with the countercurrent depressurization step assisted by a vacuumpump or similar device to evacuate the adsorption zone to reachdesorption conditions.

As noted above the more strongly adsorbed components, i.e., theadsorbate, are removed from the adsorber bed by countercurrentlydepressurizing the adsorber bed to a desorption pressure. In general,lower desorption pressures are preferred in order to provide morecomplete removal of the adsorbate during the desorption step. U.S. Pat.No. 4,338,101 discloses a process for the recovery of hydrocarbons frominert gas and hydrocarbon mixtures which includes the steps of adsorbingthe hydrocarbons in a bed of solid adsorbent and desorbing thehydrocarbons from the bed of adsorbent by evacuating the bed using avacuum pump. U.S. Pat. Nos. 5,154,735 and 5,229,089 disclose similarprocesses for recovering hydrocarbons from a hydrocarbon-air mixtureemploying further vacuum pumping steps to enhance desorption from thesolid adsorbents.

U.S. Pat. No. 4,842,621 discloses a process for separating a condensablegas from a non-condensable gas in a vacuum swing adsorption scheme whichincludes a supercharging step in which a stream relatively rich in thecondensable gas is passed through the adsorbent bed following theadsorption step to reduce the amount of condensable gas recycled to thebed in the adsorption step. The supercharging step occurs at a pressurewhich is higher than the adsorption pressure.

When the impurities are highly volatile or explosive in mixtures withair or other gases, approaches must be employed which avoid thepotential safety hazard of fire or explosion should the recovered VOCstream approach a composition in its detonation region. Processes aresought which permit the safe concentration and economic recovery ofVOC's from waste gas streams without the further dilution of the wastegas stream with inert gases which raise the capital and operating costs.

SUMMARY OF THE INVENTION

By the present invention, a VSA process is provided for the removal ofVOCs from a fluid stream that can yield a vent stream essentially freeof VOCs and recover a liquid VOC product. The process employs aselective adsorbent and a diluent. The diluent is an adsorbable inactivegas which is preloaded on the adsorbent and subsequently employed as acopurge gas in a copurge step is thus retained in the process. Byretaining the inactive gas in a closed cycle, the formation of anexplosive mixture is avoided and a higher separation efficiency isachieved at a lower cost than traditional methods.

In a broad aspect of the present invention there is provided a vacuumswing adsorption (VSA) process for the recovery and removal of VOCs froma fluid feedstream comprising VOCs and air. The process includes thesteps of passing an adsorbable inactive gas stream to a first adsorptionbed of a VSA zone comprising at least two adsorption beds to preload thefirst adsorption bed with the adsorbable inactive gas and a firstadsorption effluent stream is withdrawn. Each of the adsorption bedscontains an adsorbent selective for the adsorption of VOCs. The firstadsorption bed is countercurrently evacuated to a desorption pressure toprovide a first residual gas stream comprising the adsorbable inactivegas. The feedstream is passed to the first adsorption bed at adsorptionconditions including an adsorption pressure and an adsorptiontemperature and a second adsorption effluent stream is recovered. Aportion of the first or the second residual gas stream is cocurrentlypassed to the first adsorbent bed in a copurge step and a thirdadsorption effluent is recovered. The third adsorption effluent streamand the second adsorption effluent stream are admixed to provide atreated effluent stream depleted in VOCs relative to the feedstream. Thefirst adsorbent bed is countercurrently evacuated to the desorptionpressure to provide a tail gas comprising VOCs and the tail gas streamis separated into a VOC-containing stream and a second residual gasstream. The steps of adsorption of the VOCs from the feedstream,copurge, countercurrent evacuation, separation of the tail gas streaminto a VOC-containing stream and the residual gas stream are repeatedwith each of the adsorbent beds such that a continuous operation of theprocess is performed.

In another embodiment a vacuum swing adsorption (VSA) process isprovided for the separation and recovery of VOCs from a feedstreamcomprising VOCs and a mixture thereof with air. The VSA processcomprises a series of steps. A gas stream comprising nitrogen is passedto a first adsorption bed of a VSA zone comprising at least twoadsorption beds to preload the first adsorption bed with nitrogen and afirst adsorption effluent stream is withdrawn. Each of the adsorptionbeds contains a first adsorbent layer and a second adsorbent layer. Thefirst adsorbent layer comprises an adsorbent selective for theadsorption of VOCs. The second adsorbent layer comprises an adsorbentselective for the adsorption of nitrogen. The first adsorption bed iscountercurrently evacuated to a desorption pressure to provide a firstresidual gas stream comprising nitrogen. The feedstream is passed atadsorption conditions, including an adsorption temperature and anadsorption pressure, to the first adsorption bed and a second adsorptioneffluent stream, depleted in VOCs, is withdrawn. A portion of the firstor the second residual gas stream is cocurrently passed to the firstadsorption bed and a third adsorption effluent stream, comprisingoxygen, is withdrawn. The third adsorbent effluent stream and the secondadsorption effluent stream are admixed to provide a treated adsorptioneffluent stream having a reduced concentration of VOCs. The firstadsorption bed is countercurrently evacuated to the desorption pressureto provide a tail gas stream comprising nitrogen and VOCs. The tail gasstream comprising nitrogen and VOCs is separated into a VOC-containingstream and a second residual gas stream. The steps of adsorption of thefeedstream and cocurrently passing the residual gas stream to the firstadsorption bed and admixing the first, and second adsorption streamcountercurrent evacuation, and separating the tail gas into theVOC-containing stream and residual stream are repeated such that acontinuous operation of the VSA process is performed.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of the process of the invention for theremoval of VOCs from a fluid stream.

DETAILED DESCRIPTION OF THE INVENTION

The pressure swing adsorption process is an essentially adiabaticprocess for separating a multi-component fluid containing at least oneselectively adsorbable component. The PSA process of the inventionrelates to conventional PSA processing in which each bed of anadsorption zone undergoes, on a cyclic basis, high pressure adsorption,optional cocurrent depressurization to intermediate pressure level(s)with release of void space gas from the product end of the bed,countercurrent depressurization to lower desorption pressure with therelease of desorbed gas from the feed end of the bed, with or withoutpurge of the bed, and repressurization to higher adsorption pressure.The process of the present invention adds to this basic cycle sequencethe use of a cocurrent copurge step, or copurge step in the adsorptionzone in which the less readily adsorbable component is further andpreferably essentially completely removed therefrom by the introductionof a copurge gas. The adsorption zone is then countercurrentlydepressurized to a desorption pressure that is at or below atmosphericpressure with the more adsorbable component(s) comprising VOCs beingdischarged from the feed end thereof as a product. In the multi-bedadsorption systems to which the invention is directed, the copurge gasused for each bed is obtained by diverting a portion of the gas releasedfrom that or another bed in the system during the countercurrentdepressurization and purge steps, following recompression, or obtainedfrom an external stream which comprises an adsorbable inactivecomponent. It is preferred that the copurge gas be an external streamfor a first cycle and thereafter be a residual gas comprising anon-condensed portion of the gas released from that or another bed inthe system during the countercurrent depressurization and purge steps,following recompression and condensation to remove the liquefied VOCproduct. When the VOCs are non-condensible, the VOCs are removed in theresidual gas stream. The residual gas stream is cooled and a portion ofthe residual gas stream depleted in oxygen is returned to the adsorptionzone as a copurge gas and a portion of the residual gas comprising theVOCs is withdrawn for use as fuel, for further recovery of the VOCs orincinerated.

The VOCs may be selected from the group consisting of saturated andunsaturated hydrocarbons, oxygenated materials, halogenated materials,and mixtures thereof. The unsaturated hydrocarbons may comprise ethyleneor propylene. The oxygenated materials may be selected from the groupconsisting of alcohols, ethers, esters, aldehydes, ketones and mixturesthereof. The halogenated materials may comprise chlorinated hydrocarbonssuch as methyl chloride. The VOCs in the residual gas stream may becondensible or non-condensible at conditions following recompression andcooling.

Those skilled in the art will appreciate that the high pressureadsorption step of the PSA process comprises introducing the feedstreamto the feed end of the adsorbent bed at a high adsorption pressure. Theless readily adsorbable component(s) passes through the bed and isdischarged from the effluent end thereof. An adsorption front or frontsare established in the bed with said fronts likewise moving through thebed from the feed end toward the effluent end thereof. When thefeedstream contains a less readily adsorbable component and a morereadily adsorbable component, a leading adsorption front of the morereadily adsorbable component will be established and move through thebed in the direction of the effluent end thereof. In the process of thisinvention it was discovered that the different components were adsorbedto different degrees. For example, if the most readily adsorbablespecies were the VOCs, a more readily adsorbable component was nitrogen,and the least readily adsorbable component was oxygen, during theadsorption step, the oxygen would initially become adsorbed on theadsorbent. As the mass transfer front proceeded through the bed, thenitrogen would be co-adsorbed on the adsorbent, displacing a portion ofthe oxygen.

The feedstream of this invention is generally an industrial waste gasand comprises from about 0.01 to about 20 mol % VOCs, and from about 50to 99.9 mol % air. The feedstream may comprise water up to saturationconditions. The feedstream is charged to an adsorption zone to recoverVOCs and provide a treated adsorption effluent, depleted in VOCs. In theadsorption zone, the most readily adsorbable component, VOCs, isadsorbed at an adsorption pressure and an adsorption temperature, andthe less readily adsorbable components are passed through the adsorptionzone and are withdrawn in an adsorption effluent. The adsorption zonepressure ranges from about 100 to about 3450 kPa (about 15 to about 500psia). The adsorption zone temperature is any temperature effective toadsorb the more readily adsorbable components in the feedstream, andpreferably from about -18° C. to about 205° C. (about 0° to about 400°F.). It is to be understood that the adsorption zone of the presentinvention contains adsorption beds containing adsorbent suitable foradsorbing the particular components to be adsorbed therein. As thecapacity of the adsorption bed for the most readily adsorbable componentis reached; that is, preferably before a substantial portion of theleading adsorption front has passed through the first adsorption bed,the feedstream is directed to another bed in the adsorption zone. It isto be also understood that the term "countercurrent" denotes that thedirection of gas flow through the adsorption zone, i.e., adsorber bed,is countercurrent with respect to the direction of feedstream flow.Similarly, the term "cocurrent" denotes flow in the same direction asthe feedstream flow. The purge gas is at least partially comprised of aneffluent stream, e.g., the adsorption effluent stream or the copurgeeffluent stream from the adsorption zone, as hereinafter described,which comprises the less readily adsorbable component. When nitrogen isthe less readily adsorbable component, the purge gas is preferablyenriched in nitrogen at a higher concentration than available in thefeedstream. The term "enriched" is intended to be with reference to thefeedstream composition unless otherwise noted. A copurge gas is passedthrough the bed in a direction cocurrent to the feeding step. By the useof a copurge gas substantially reduced and preferably essentially freeof the less readily adsorbable component, thus having a molarconcentration of more readily adsorbable components, the less readilyadsorbable component that remains in the void spaces of the adsorptionbed ahead of the leading adsorption front can be essentially completelydisplaced from the bed. This enables the most readily adsorbablecomponent to be thereafter discharged from the feed end of the bed as aproduct by countercurrently depressurizing the bed. The copurge step canbe performed in conjunction with one or more cocurrent depressurizationsteps. When a cocurrent depressurization step is used, it can beperformed either before, simultaneously with, or subsequent to thecopurge step. The effluent stream from the cocurrent depressurizationstep, which is comprised primarily of less readily adsorbablecomponents, can be used to partially repressurize or purge anotheradsorption bed. Preferably, a portion of the adsorption effluent fromthe latter part of the copurge step is used as the purge feed. At thispoint in the cycle, the effluent from the copurge step is reduced inoxygen.

After the termination of the copurge step and any desired cocurrentdepressurization step(s), the adsorption bed is desorbed by reducing thepressure in a direction countercurrent to the feeding direction to adesorption pressure that is preferably from about 3 kPa (0.5 psia) toabout 345 kPa (about 50 psia), and more preferably a desorption pressurethat ranges from about 3 kPa (0.5 psia) to about 138 kPa (20 psia). If apurge step is used, the oxygen reduced effluent produced during thelatter portion of the copurge step is used to purge the adsorption bedto ensure that the desorption effluent, or tail gas, is non-explosive.Following recompression, a portion of the desorption effluent streamrecovered from the adsorption zone could be utilized as copurge gas forthe copurge step. If the VOC's are condensible, the desorption effluent,following compression and condensation of VOCs is used as the residualor copurge gas. When the VOCs are non-condensible, a portion of thedesorption effluent following recompression is employed as the residualor copurge gas.

A VSA cycle for a 3 bed adsorption zone employing a copurge step isshown in Table 1 below.

                  TABLE 1    ______________________________________    Bed No. Cycle    ______________________________________    1       R           A               C           V                                P                                2  V  P R  A   C                                3  C    V  P R  A    ______________________________________

In the above table, A represents an adsorption step at adsorptionpressure and temperature, with the feedstream being introduced to thefeed end of an adsorption bed in the adsorption zone and the lessreadily adsorbable components being discharged from the effluent endthereof. In the present invention the feedstream enters the adsorptionbed at the feed end, the VOCs are adsorbed, and a VOC-reduced stream isproduced at the effluent end of the adsorption bed. C represents copurgeby the introduction of gas essentially free of the less readilyadsorbable component to the feed end of the bed so as to further, andpreferably essentially completely displace said less readily adsorbablecomponent from the bed. The copurge step may be performed at constant orvarying pressure. P represents a purging step at low pressure in theadsorption zone; R represents a repressurization step wherein a processgas such as the feedstream or a portion of the adsorption effluent fromthe adsorption step or the copurge step is utilized to repressurize theadsorber bed to the adsorption pressure. V represents a vacuum orevacuation step wherein the pressure of the adsorption bed is reduced tothe desorption pressure with a vacuum pump or similar device. Adesorption effluent or tail gas comprising the most readily adsorbableand the more readily adsorbable components is withdrawn during thisstep. It will be understood that in addition to the three-bedconfiguration illustrated above for the adsorption zone, otherconfigurations, i.e., 2, 4, 5 or more beds, can be employed and areintended to be within the scope of the present invention.

The copurge step may also occur following a cocurrently depressurizingstep and prior to a further cocurrently depressurizing step. In thecopurge step, a second feed or copurge gas is cocurrently passed to theadsorption zone forcing additional unadsorbed material from theadsorption zone. The copurge gas must have a concentration of the morereadily adsorbable components which is greater than the concentration ofthe more readily adsorbable component in the first feed. Typically, thisadditional unadsorbed material withdrawn in the copurge step is combinedwith the effluent from the adsorption step. The effluent withdrawn fromthe adsorbent bed during the copurge step, is initially VOC-free air.During the latter part of the copurge step, the effluent withdrawn fromthe adsorbent bed is oxygen-lean. This oxygen-lean effluent may be usedas a purge gas.

It will further be understood that various changes and modifications canbe made in the details of the VSA process with intermediate productrecovery as herein described and illustrated above without departingfrom the scope of the invention as set forth in the appended claims.Accordingly, the individual steps described, as well as conventionalvariations thereof are generally known by those skilled in the art andneed not be further described herein. It will be further understood thatVSA systems necessarily incorporate various conduits, valves, and othercontrol features to accomplish the necessary switching of adsorbent bedsfrom one step to the next, in appropriate sequence as in conventionalVSA operations.

It will also be understood that the invention can be carried out usingany suitable adsorbent material in the adsorption zone having aselectivity for various components of a feedstream over other suchcomponents, thereby providing a less readily adsorbable component and amore readily adsorbable component. Suitable adsorbents known in the artand commercially available include crystalline molecular sieves,activated carbons, activated clays, silica gels, activated aluminas andthe like. Such adsorbent material or mixtures thereof will be understoodto be suitable if the adsorbent material is capable of selectivelyadsorbing impurities such as VOCs and water from a fluid stream. Themolecular sieves include, for example, the various forms ofsilicoaluminophosphates, and aluminophosphates disclosed in U.S. Pat.Nos. 4,440,871; 4,310,440 and 4,567,029, hereby incorporated byreference as well as zeolitic molecular sieves.

As used here, the term "molecular sieve" is defined as a class ofadsorptive desiccants which are highly crystalline in nature, distinctfrom amorphous materials such as gamma-alumina. Preferred types ofmolecular sieves within this class of crystalline adsorbents arealuminosilicate materials commonly known as zeolites. The term "zeolite"in general refers to a group of naturally occurring and synthetichydrated metal aluminosilicates, many of which are crystalline instructure. There are, however, significant differences between thevarious synthetic and natural materials in chemical composition, crystalstructure and physical properties such as x-ray powder diffractionpatterns. The zeolites occur as agglomerates of fine crystals or aresynthesized as fine powders and are preferably tableted or pelletizedfor large-scale adsorption uses. Pelletizing methods are known which arevery satisfactory because the sorptive character of the zeolite, bothwith regard to selectivity and capacity, remains essentially unchanged.

The pore size of the zeolitic molecular sieves may be varied byemploying different metal cations. For example, sodium zeolite A has anapparent pore size of about 4 Å units, whereas calcium zeolite A has anapparent pore size of about 5 Å units. The term "apparent pore size" asused herein may be defined as the maximum critical dimension of themolecular sieve in question under normal conditions. The apparent poresize will always be larger than the effective pore diameter, which maybe defined as the free diameter of the appropriate silicate ring in thezeolite structure.

Zeolitic molecular sieves in the calcined form may be represented by thegeneral formula;

    Me.sub.2/n O:Al.sub.2 O.sub.3 :xSiO.sub.2 :yH.sub.2 O

where Me is a cation, x has a value from about 2 to infinity, n is thecation valence and y has a value of from about 2 to 10. Typicalwell-known zeolites which may be used include chabazite, also referredto as Zeolite D, clinoptilolite, erionite, faujasite, also referred toas Zeolite X and Zeolite Y, ferrierite, mordenite, Zeolite A, andZeolite P. Other zeolites suitable for use according to the presentinvention are those having a high silica content, i.e., those havingsilica to alumina ratios greater than 10 and typically greater than 100.One such high silica zeolite is silicalite, as the term used hereinincludes both the silicapolymorph disclosed in U.S. Pat. No. 4,061,724and also the F-silicate disclosed in U.S. Pat. No. 4,073,865, herebyincorporated by reference. Detailed descriptions of some of theabove-identified zeolites may be found in D. W. Breck, Zeolite MolecularSieves, John Wiley and Sons, New York, 1974, hereby incorporated byreference.

The general formula for a molecular sieve composition known commerciallyas type 13X is:

    1.0±0.2Na.sub.2 O:1.00A1.sub.2 O.sub.3 :2.5±0.5SiO.sub.2

plus water of hydration. Type 13X has a cubic crystal structure which ischaracterized by a three-dimensional network with mutually connectedintracrystalline voids accessible through pore openings which will admitmolecules with critical dimensions up to 10 Å. The void volume is 51volume percent of the zeolite and most adsorption takes place in thecrystalline voids.

It is often desirable when using crystalline molecular sieves that themolecular sieve be agglomerated with a binder in order to ensure thatthe adsorbent will have suitable physical properties. Although there area variety of synthetic and naturally occurring binder materialsavailable such as metal oxides, clays, silicas, aluminas,silica-aluminas, silica-zirconias, silica-thorias, silica-berylias,silica-titanias, silica-alumina-thorias, silica-alumina-zirconias,mixtures of these and the like, clay-type binders are preferred.Examples of clays which may be employed to agglomerate the molecularsieve without substantially altering the adsorptive properties of thezeolite are attapulgite, kaolin, volclay, sepiolite, palygorskite,kaolinite, bentonite, montmorillonite, illite and chlorite. The choiceof a suitable binder and methods employed to agglomerate the molecularsieves are generally known to those skilled in the art and need not befurther described herein.

The process of this invention is illustrated in FIG. 1. FIG. 1 is aschematic flow sheet of a vacuum swing adsorption process for theremoval of VOCs and water, if present, from a mixture thereof with airaccording to the instant invention. With reference to FIG. 1, the threeadsorption beds 101,102, and 103 are loaded with a silica gel adsorbentand arranged in parallel between feedstream manifold 10 and effluentmanifold 28. The full cycle will be described for adsorption bed 101 andis typical for all adsorption beds. Assume adsorption bed 101 ispressurized with air, although the adsorption beds may be pressurizedwith nitrogen, and that all its associated valves are initially closed.Pressures and times are illustrative. Valve 110 opens and an initialcharge of an adsorbable inactive gas stream in line 30 such as nitrogen,argon, carbon monoxide, methane, or carbon dioxide is cocurrently passedto adsorption bed 101 at adsorption conditions including an adsorptionpressure and an adsorption temperature via lines 30, 34, 35, valve 110,line 36 and line 16. An adsorption effluent, comprising oxygen iswithdrawn from the adsorption zone via line 20, valve 119 and passed tothe effluent header 28 via line 22. Flow continues until the adsorbableinactive gas stream has displaced oxygen from the adsorption bed. Nowvalves 110 and 119 close and valve 112 opens, thereby establishing thebeginning of the countercurrent evacuation step to the desorptionpressure which is established by vacuum pump 126. The desorptioneffluent, or tail gas stream, which is oxygen-lean and thereforenon-explosive, is passed to the vacuum pump via lines 16 and 60, valve112, line 58, line 70 and line 74. From the vacuum pump, the tail gasstream is passed via line 76 to chiller 105 where the temperature of thetail gas is reduced to condense at least a portion of the water andpassed to condenser 104 via line 78 wherein the vapor and liquid phasesare separated to provide a residual gas stream which is depleted inoxygen relative to the feedstream in line 32 and a condensed waterstream in line 80 which is recovered. If no condensed water is presentand the VOCs are non-condensible, the residual gas stream comprises aportion of the tail gas stream. Following the evacuation step, valves120 and 122 open to begin the purge step. As the desorption effluent ispassed to the vacuum pump, a portion of an oxygen-free, VOC-free, secondadsorption effluent is permitted to flow as a purge gas from adsorptionbed 102 which is nearing the completion of its copurge step. This purgegas flows from adsorption bed 102 via lines 50 and 42, valve 122, lines44 and 40, valve 120 and lines 38 and 18. At the conclusion of the purgestep, the adsorption bed 101 undergoes repressurization. Valves 120 and112 close and valve 111 opens allowing the feedstream from the feedheader 10 to be passed through line 12, valve 111 and lines 14 and 16 tothe adsorption bed 101. When the pressure in adsorption bed 101 reachesthe adsorption pressure, valve 119 opens and the adsorption step begins.During the adsorption step, the feedstream continues to be passed toadsorption bed 101, but now a first adsorption effluent is withdrawnfrom the adsorption bed to the effluent header 28 via lines 18 and 20,valve 119 and line 22.

At the conclusion of the adsorption step, adsorption bed 101 undergoes acopurge step, wherein valve 111 is closed and valve 110 opens, allowinga portion of the residual gas in line 32 to be passed to the adsorptionbed 101 via lines 34 and 35, valve 110 and lines 36 and 16. During thiscopurge step a second adsorption effluent is passed via lines 18 and 20,valve 119, and line 22 to the effluent header.

The other adsorption beds are operated in a similar fashion according tothe cycle shown in Table 1. For adsorption bed 102, during theadsorption step, the feedstream is passed to adsorption bed 102 vialines 10 and 48, valve 114 and lines 49 and 82. Similarly, foradsorption bed 103, during the adsorption step, the feedstream is passedto adsorption bed 103 via lines 10 and 52, valve 117 and lines 54 and84. The first adsorption effluent is withdrawn from adsorption bed 102via line 50, valve 121, and line 24 to reach the effluent header 28.Similarly, for adsorption bed 103 in the adsorption step, the feedstreamis passed from the feed header 10 to line 52, valve 117, line 54, andline 84, while the first adsorption effluent is passed to the effluentheader 28, via line 56, valve 123, and line 26. During the copurge step,the residual gas stream is passed to adsorption bed 102 via line 34,line 37, line 62, valve 113, line 64, and line 82. Similarly, foradsorption bed 103, the copurge gas stream is passed to adsorption bed103 via line 34, line 37, line 68, valve 116, line 67, and line 84.During the evacuation step for adsorption bed 102, the desorptioneffluent is withdrawn via line 82, line 66, valve 115, line 65, line 70and line 74 to reach the vacuum pump 126. Toward the end of theevacuation step, purge gas from adsorption bed 103 is passed via line56, line 46 valve 124, line 45, line 44, valve 122, line 42, and line50. Similarly, for adsorption bed 103 during the evacuation step, thedesorption effluent is withdrawn via line 84, line 72, valve 118, line73 and line 74 to reach the vacuum pump 126. During the purge step,purge gas from adsorption bed 101 is passed to adsorption bed 103 vialine 18, line 38, valve 120, line 40, line 45, valve 124, line 46 andline 56.

Adsorption beds 102 and 103 may be initially preloaded with nitrogen oran inactive gas from line 30 in turn in the same fashion as adsorptionbed 101, prior to the introduction of the feedstream. Under normaloperation, the initial preloading of the first adsorption bed withinactive gas is sufficient to sweep the oxygen from the adsorption bedsduring the copurge step to maintain a closed cycle of the inactive gas.Should the feedstream composition be sufficiently lean with respect tothe inactive gas, a second adsorbent layer, containing an adsorbent suchas zeolite X, zeolite Y, silicates, high silica zeolites and mixturesthereof, selective for the adsorption of the inactive gas may be placeddownstream of a first adsorbent layer, wherein the first adsorbent layeris selective for the adsorption of VOCs. The first and the secondadsorbent layers may be located in the same adsorption bed. Thus, theadsorbent in the second adsorbent layer acts to retain the inactive gaswithin the adsorbent bed in a closed cycle in order to prevent theformation of an explosive mixture of VOCs in the tail gas stream or inthe residual gas stream. In this configuration, the process may beoperated for several cycles as an air separator to provide theadsorbable inactive gas stream. Air is passed to the process withoutintroducing the feedstream until the residual gas stream is depleted inoxygen. At that point, the preloading of inactive gas will be completeand the feedstream introduced to the adsorption bed.

By employing the copurge step in the PSA zone to displace the adsorbedoxygen with an adsorbable inactive gas, the composition of the VOC-rich,tail gas stream will remain below the lower explosive limit of the VOCsin the tail gas stream. In starting up the process, the copurge gas maybe supplied as an initial charge from an outside source of say,nitrogen. Following this initial charge, the amount of nitrogen returnedin the residual gas should be sufficient to displace the oxygen in theadsorption bed and to maintain the tail gas below the lower explosivelimit. Preferably, for most feedstream compositions, the initialdisplacement gas charge will range from about 1 to about 20 percent ofthe feed rate per cycle, and more preferably the initial displacementgas charge will range between about 8 to about 20 percent of the feedrate per cycle. Since the external inactive gas stream in line 30 isused as the copurge gas for the first cycle, the residual gas in line 32may be vented to the atmosphere or admixed with the feedstream duringthe first copurge step. Following the first cycle, the residual gasstream in line 32 is employed as the copurge gas, the residual gas beingreduced in oxygen.

The invention will be further clarified by a consideration of thefollowing examples, which are intended to be purely exemplary of the useof the invention. These examples are based on engineering designcalculations.

EXAMPLES Example I

A feed gas mixture representing an air-VOC mixture containing 79%nitrogen, 20.8% oxygen and 0.2% xylene was treated in a typical 3-bedvacuum swing adsorption (VSA) process. Each of the adsorption bedscontained silica gel adsorbent. The feed gas was charged to theadsorption beds at a temperature of about 32° C. (90° F.) and a pressureof 138 kPa (20 psia) in the amount of 1,000 pound-moles per hour. Underconventional VSA processing, the adsorption step producing a treatedadsorption effluent gas, depleted in VOCs, was followed bydepressurization and/or evacuation steps to reduce the pressure in theadsorption bed to desorption conditions, producing a VOC-rich tail gasstream. The VSA recovered about 90% of the air per cycle. Upon thecooling and condensation of the tail gas stream, a residual gas streamand a condensed VOC stream were produced. The average composition of theVOC-rich gas stream, or tail gas stream, desorbed from the adsorbent andthe residual gas stream following condensation of VOC's is shown inTable 2. This residual gas stream is either recombined with the feed gasor used as a copurge gas following the adsorption step. Unfortunately,the composition of the VOC-rich gas stream having 20% O₂ and 2% xyleneis within the explosive range, and therefore this operation is notviable, despite its ability to produce treated adsorption effluent gassignificantly depleted of VOCs relative to the feed gas stream,containing less than about 10 ppm-mol of xylene. The lower and upperexplosive limits (LEL and UEL) for xylene air is 1 and 7 vol %,respectively.

EXAMPLE II

In Example II, the feed gas of Example I was charged to a VSA processsimilar to Example I, based on an air recovery reduced from that ofExample I to about 70% so that the VOC-rich gas is not explosive. Thelower efficiency requires the operation at a higher desorption pressureof about 34 kPa (5 psia) compared to the desorption pressure of about 14kPa (2 psia) in Example I. In Example II, the VOC-rich gas and theresidual gas flow rates were 4 times greater than those of Example I.Therefore, this Example II operation at 70% air recovery per cyclerequired a larger vacuum pump than Example I and a condenser 2 timeslarger than Example I. The vacuum pump of Example II required over 2times the power of Example I to achieve the same separation. TheVOC-rich gas produced in Example II is not explosive because the VOCconcentration is less than the lower explosive limit (LEL), which is 1.0mol-% xylene in air.

EXAMPLE III

The feed gas mixture of Example I was charged to the process of thepresent invention. As in Example I, the adsorbent was silica gel and theVSA zone contained 3 adsorption beds. Nitrogen in the amount rangingfrom about 8 to about 20 percent of the feed rate was employed toinitially copurge the first adsorption bed to preload the adsorbent bedand to provide a sufficient amount of nitrogen to the system to preventthe formation of an explosive mixture on desorption of the adsorptionbed. The results of this operation are shown in the table. Surprisingly,the oxygen content of the VOC-rich gas was reduced dramatically to about1.0%, while the VSA system operated at about a 90% recovery of air percycle. Thus, the preloading of the adsorption bed with nitrogen duringthe first cycle and the closed cycle operation maintained the VOC-richgas stream and the residual gas stream outside explosive limits.Furthermore, the amount of residual gas in Example III was returned tothe level of Example I with a correspondingly lower power requirementfor the vacuum pump over Example II.

                                      TABLE 2    __________________________________________________________________________    COMPARISON OF VSA OPERATION FOR VOC RECOVERY             Example I                      Example II                               Example III             VOC Residual                      VOC Residual                               VOC Residual    __________________________________________________________________________    P, PSIA  2-20                 20   5-20                          20   2-20                                   20    T, °F.             80  40   80  40   80  40    F, lb Moles             113 111  430 428  113 111    Composition,    N.sub.2  77.5                 79.0 78.7                          79   97.0                                   98.8    O.sub.2  20.5                 20.8 20.6                          20.8 1.0 1.0    Xylene   2.0*                 0.2  0.7 0.2  2.0 0.2    Vacuum pump,             185      440      185    __________________________________________________________________________     *Explosive Mixture

EXAMPLE IV

A feed gas mixture comprising air and a VOC containing 76.1 vol %nitrogen, 20.2 vol % oxygen, 3.6 vol % water and about 500 ppm-volethylene, a non-condensible VOC, was treated in a typical 3-bed vacuumswing adsorption (VSA) process. Each adsorption bed had a feed end andan effluent end. Each of the adsorption beds contained a first layer ofsilica gel adsorbent and a second layer of a nitrogen selectiveadsorbent, zeolite 13X. The layer of the nitrogen selective adsorbentwas located at the effluent end, typically the top, of each adsorptionbed. As in Example III, a stream of nitrogen was employed to initiallypreload the adsorption beds with nitrogen and to provide a sufficientamount of nitrogen in the 3-adsorption bed system to prevent theformation of an explosive mixture of air and the VOCs. In this Example,only a portion of the water condensed at the temperature of thecondenser which ranged from about 15° C. (60° F.) to about 27° C. (80°F.). The results of Example IV are shown in Table 3. The adsorptioneffluent, or treated feed gas, contained less than 10 ppm-mol ethylene.The VOCs, as shown by the ethylene composition, remained in the residualgas stream. The oxygen content of the residual gas stream was about 1%,well below the explosive limit and permitting at least a portion of theresidual gas stream to be employed as the nitrogen-rich copurge streamand a portion to be withdrawn as a product, comprising the VOC. Theproduct portion of the residual gas stream, now containing aconcentrated amount of ethylene, can be returned to an ethyleneproduction process for further recovery of the ethylene from thenitrogen, or recovered for incineration or fuel use. The recoveredresidual gas stream contained about 0.4 vol-% ethylene.

                                      TABLE 3    __________________________________________________________________________    CONCENTRATION OF STREAMS WITH NON-CONDENSIBLE VOCs             Feed Gas                  Adsorption Effluent                            Condensate                                  Residual Gas    __________________________________________________________________________    Pressure, kPa             172  103       103   158    Composition,    Mol %    Nitrogen 76.1 76.4            94.5    Oxygen   20.2 23.6            1.0    Ethylene, ppm             500  10              4440    Water    3.6            100   4.0    __________________________________________________________________________

EXAMPLE V

A feed gas mixture containing air, ethylene, and water was charged to a3-bed VSA process to produce a vent stream containing less than about 10ppm mol ethylene as in Example IV. The composition of the feed gasmixture was 76.1 mol % nitrogen, 20.2 mol % oxygen, 3.6 mol % water and1000 ppm-mol ethylene. The feed gas was saturated with water at about37° C. and about 193 kPa. The residual gas stream produced upondesorption, cooling, and condensation of water contained about 1 mol-%oxygen, 94.1 mol-% nitrogen, 4. mol-% water, and about 8900 ppm-molethylene. A portion of the residual gas stream, equal to about 30 vol %of the feed gas mixture, was recycled to the VSA unit as a copurge gas.The remaining portion of the residual gas stream was returned to anethylene plant prior to the low temperature recovery section for therecovery of the ethylene.

We claim:
 1. A vacuum swing adsorption (VSA) process for the separationand recovery of VOCs from a feedstream comprising VOCs and mixturesthereof with air, said process comprising the following steps:a) passingan adsorbable inactive gas stream to a first adsorption bed of a VSAzone comprising at least two adsorption beds each of said adsorptionbeds containing an adsorbent selective for the adsorption of said VOCsto preload said first adsorption bed with said adsorbable inactive gasand withdrawing a first adsorption effluent stream; b) countercurrentlyevacuating said first adsorption bed to a desorption pressure to providea first residual gas stream comprising said adsorbable inactive gas; c)passing said feedstream to said first adsorption bed at adsorptionconditions including an adsorption pressure and an adsorptiontemperature and recovering a second adsorption effluent stream; d)cocurrently passing a portion of the first or a second residual gasstream in a copurge step to said first adsorption bed and producing athird adsorption effluent stream; e) admixing said third adsorptioneffluent stream and said second adsorption effluent stream to provide atreated adsorption effluent stream depleted in VOCs relative to thefeedstream; f) countercurrently evacuating said first adsorption bed tosaid desorption pressure to provide a tail gas stream comprising saidVOCs and separating said tail gas stream into a VOC-containing streamand the second residual stream; and g) repeating steps (c) through (f)with each of said adsorption beds such that a continuous operation ofthe process is performed.
 2. The process of claim 1 wherein theadsorbable inactive gas stream contains an adsorbable inactive componentselected from the group consisting of nitrogen, carbon dioxide, carbonmonoxide, argon, methane, and mixtures thereof.
 3. The process of claim1, wherein the adsorbable inactive gas stream comprises nitrogen.
 4. Theprocess of claim 1, wherein the adsorbent selective for the adsorptionof said VOCs is selected from the group consisting of aluminas, silicagel, activated alumina, activated carbon, molecular sieves and mixturesthereof.
 5. The process of claim 1 wherein the adsorption beds comprisea first adsorbent layer selective for the adsorption of said VOCs and asecond adsorbent layer selective for the adsorption of said VOCs andsaid adsorbable inactive gas stream.
 6. The process of claim 5 whereinsaid adsorbable inactive gas comprises nitrogen.
 7. The process of claim5 wherein said first adsorbent layer contains an adsorbent selected fromthe group consisting of aluminas, silica gel, activated alumina,activated carbon, molecular sieves, and mixtures thereof.
 8. The processof claim 5 wherein the first adsorbent layer comprises silica gel. 9.The process of claim 5 wherein said second adsorbent layer is selectedfrom the group consisting of zeolite X, zeolite Y, silicalites andmixtures thereof.
 10. The process of claim 9 wherein said secondadsorbent layer comprises zeolite 13X.
 11. The process of claim 1further comprising the step of purging said first adsorption bedfollowing step (b) with a purge gas comprising a portion of said firstadsorption effluent.
 12. The process of claim 11 wherein said portion ofsaid first adsorption effluent is withdrawn during a latter portion ofsaid copurge step.
 13. The process of claim 12 further comprising arepressurization step that occurs following said purge step wherein saidfirst adsorption bed is partially repressurized with a portion of arepressurization gas comprising said first adsorption effluent.
 14. Theprocess of claim 1 wherein said second residual gas stream is depletedin oxygen relative to the feedstream.
 15. The process of claim 1 whereinsaid adsorption temperature ranges from about -18° C. (0° F.) to about205° C. (400° F.).
 16. The process of claim 1 wherein the adsorptionpressure ranges from about 100 kPa (15 psia) to about 3450 kPa (500psia).
 17. The process of claim 1 wherein the desorption pressure rangesfrom about 14 kPa (0.5 psia) to about 138 kPa (20 psia).
 18. The processof claim 1 wherein said VSA zone contains at least 3 adsorption beds.19. A vacuum swing adsorption (VSA) process for the separation andrecovery of VOCs from a feedstream comprising VOCs, and a mixturethereof with air, said VSA process comprising the following steps:a)passing a gas stream comprising nitrogen to a first adsorption bed of aVSA zone comprising at least two adsorption beds, each of saidadsorption beds containing a first adsorbent layer and a secondadsorbent layer, said first adsorbent layer comprising an adsorbentselective for the adsorption of VOCs, said second adsorbent layercomprising an adsorbent selective for the adsorption of nitrogen, topreload said first adsorbent bed with nitrogen and withdrawing a firstadsorption effluent; b) countercurrently evacuating said firstadsorption bed to a desorption pressure to provide a first residual gasstream comprising nitrogen; c) passing said feedstream at adsorptionconditions including an adsorption temperature and an adsorptionpressure to said first adsorption bed and withdrawing a secondadsorption effluent stream depleted in VOCs; d) cocurrently passing aportion of the first or a second residual gas stream to said firstadsorption bed and withdrawing a third adsorption effluent comprisingoxygen; e) admixing said third adsorption effluent stream and saidsecond adsorption effluent stream to provide a treated adsorptioneffluent stream having a reduced concentration of VOCs; f)countercurrently evacuating said first adsorption bed to the desorptionpressure to provide a tail gas stream comprising nitrogen and VOCs; g)separating said tail gas into a VOC-containing stream and the secondresidual gas stream; and h) repeating steps (c) through step (g) suchthat a continuous operation of said process is performed.
 20. Theprocess of claim 19 wherein the feedstream comprises VOCs, air andwater.
 21. The process of claim 19 wherein the gas stream comprisingnitrogen of step (a) is an initial displacement gas charge which rangesfrom about 1 to about 20 percent of the feedstream passing in step (c).22. The process of claim 19 wherein the treated adsorption effluentcomprises less than 10 ppm-mol VOCs.
 23. The process of claim 19 whereinthe feedstream comprises between about 0.01 to about 20 mol-% VOC's andfrom about 50 to about 99.9 mol-% air.
 24. The process of claim 19wherein the feedstream comprises water up to saturation.
 25. The processof claim 19 wherein said gas stream comprises air and steps (a) through(b) and (e) are repeated until said first residual gas stream isdepleted in oxygen before proceeding with step (c).